Possing excellent catalytic performance about counter electrode (CE) is the prerequisite for obtaining high performance dye sensitized solar cells (DSSCs). Herein, The NiCo2S4/carbon nanofibers (NiCo2S4/CNFs) are successfully synthetised via hydrothermal and electrospinning method, and then directly used in DSSCs. Owing to the synergistic effect between the catalytic of NiCo2S4 materials and the electrical conductivity of CNFs, All chemical measurements reveal that NiCo2S4/CNFs applied in DSSCs exhibit good power conversion efficiency (9.0%) and stability, which surpass that of DSSCs with Pt CE (7.48%), indicating that NiCo2S4/CNFs composite would be helpful for the low-cost and efficient application of DSSCs.